Coating composition for leather, coating method, and coated leather

ABSTRACT

A paint composition for leather comprising a fluorine-containing resin and a silicone oil, and a paint composition for leather comprising a curable fluorine-containing resin, a curing agent and a silicone oil can have both soft feeling of a leather itself and film properties such as soil resistance and abrasion resistance.

FIELD OF THE INVENTION

The present invention relates to a coating composition for leather, acoating method and a coated leather.

BACKGROUND ART

A resin coating used for the surface finishing of a leather is conductedfor the prevention of penetration of soil and easy wipe-off of attachedsweat and soil, in addition to the protection of leather surface andbeautification of appearance. As a surface coating film material for theleather, used are urethane resins, nitrocellulose lacquers, proteinssuch as casein, and fluorine-free resins such as higher fatty acid esterwaxes. Among them, the urethane resins are widely used, because they areexcellent in the coating film adherence, the softness, the transparency,the bend resistance, the low-temperature resistance, the chemicalresistance, the heat resistance and the abrasion resistance.

However, conventional coating films are either hydrophilic orlipophilic, and an aqueous soil such as a mud and a soy sauce easilyattaches to the hydrophilic coating film and an oily soil such as a skinfat, a lipstick and a ball point pen ink easily attaches to thelipophilic coating film and it is difficult to remove off these soils.

On the other hand, the coating of a fluororesin paint is applied tovarious substrates such as construction materials in view of theexcellent soil resistance of the coating film. However, because thecoating film is poor in softness, the fluororesin paint is notpractically used for the leather which requires high softness.

For example, JP-A-4-279612 discloses a fluororesin coating compositionand JP-A-10-147746 discloses a composition comprising a repellent suchas a polyfluorinated carbon chain-containing compound and a siliconeoil, as a fluororesin paint. However, these documents do not considerthe leather use.

JP-A-2000-54000 discloses a leather having good soil resistance causedby applying a fluororesin paint to the leather, but the applied leatheris not one satisfying all of the demand peculiar to leather such asfeeling and matt appearance, and film properties such as soil resistanceand abrasion resistance.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a paint composition forhides and skin, which satisfies both (i) feeling and matt appearancepeculiar to hide and skin, and (ii) film properties such as soilresistance and abrasion resistance.

The present invention relates to a paint composition for leather, whichcomprises a fluororesin and a silicone oil, or which comprises a curablefluororesin, a curing agent and a silicone oil.

The coating composition of the present invention may contain a mattingagent.

According to the present invention, the feeling and the softnessessential to the leather can be maintained, the leather can besufficiently matted and the excellent soil resistance and abrasionresistance can be imparted.

EMBODIMENT FOR CARRYING OUT THE INVENTION

The fluororesin is a polymer of at least one fluoroolefin monomer, andmay be a copolymer further containing a vinyl monomer. That is, thefluororesin is a polymer of the fluoroolefin monomer(s) or a polymer ofthe fluoroolefin(s) and the vinyl monomer(s). The vinyl monomer is afluorine-containing vinyl monomer or a fluorine-free vinyl monomer.

The fluororesin may be either curable or non-curable. When thefluororesin is curable, the paint composition contains a curing agent.

The curable fluororesin has a curing reactive group. Examples of thecuring reactive group of the curable fluororesin include a hydroxylgroup, an amino group, an epoxy group, carboxyl group, mercapto group, ahydrolyzable silyl group (e.g., a trimethoxy silyl group and a triethoxysilyl group), an amide linkage, a urethane linkage and a urea linkage.The hydroxyl group is particularly preferable in view of the resinstability and the curing reactivity. The amount of the reactive groupmay have an upper limit of generally 0.5 mol, usually 0.4 mol, forexample 0.35 mol, particularly 0.2 mol, and a lower limit of generally0.001 mol, for example 0.005 mol, particularly 0.01 mol, based on 100 gof the curable fluororesin. When the reactive group is, for example, ahydroxyl group, the hydroxyl group is possessed preferably at a hydroxylgroup value of at most 200 mg KOH/g.

The curable fluororesin is generally a copolymer between thefluoroolefin monomer and the vinyl monomer.

The vinyl monomer to be copolymerized with the fluoroolefin monomer is(1) only the vinyl monomer having curing reactive group, or (2) acombination of the vinyl monomer having curing reactive group and avinyl monomer having no curing reactive group.

The amount of the fluoroolefin monomer is preferably at least 20 mol %,particularly from 20 to 60 mol %, based on the amount of thefluororesin.

The fluoroolefin monomer derives a fluoroolefin repeating unitconstituting the fluororesin. The fluoroolefin repeating unit ispreferably at least one of a chlorotrifluoroethylene (CTFE) unit, atetrafluoro ethylene (TFE) unit, a trifluoroethylene (TrFE) unit, ahexafluoropropylene (HFP) unit, a vinylidene fluoride (VDF) unit orvinyl fluoride (VF) unit.

Examples of the vinyl monomer to be copolymerized with the fluoroolefinmonomer include (i) a β-methyl-β-alkyl-substituted α-olefin, (ii) avinyl group-containing ether, and (iii) a vinyl group-containing ester.

The monomers (i), (ii) and (iii) may be a curing reactivegroup-containing vinyl monomer.

The β-methyl-β-alkyl-substituted α-olefin (i) may be, for example, acompound of the formula:CH₂═CR⁰(CH₃)wherein R⁰ is an alkyl group having 1 to 8 carbon atoms.

Specific examples of the monomer (i) include isobutylene,2-methyl-1-butene, 2-methyl-1-pentene and 2-methyl-1-hexene.

The vinyl group-containing ether (ii) may be, for example, an alkylvinyl ether or alkyl allyl ether of the formula:CH₂═CHRwherein R is OR¹¹ or CH₂OR¹¹ (R¹¹ is an alkyl group having 1 to 8 carbonatoms). When the vinyl group-containing ether (ii) has the hydroxylgroup in the form of a hydroxyalkyl vinyl ether or a hydroxyalkyl allylether (In this case, R¹¹ is an alkyl group containing the hydroxylgroup.), said hydroxyl group acts as a site reacting with the curingagent mentioned below.

The vinyl group-containing ether (ii) is not limited and specificexamples thereof include ethyl vinyl ether, butyl vinyl ether, hexylvinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether,3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether,2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether,4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether,6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutylallyl ether, and glycerol monoallyl ether.

The vinyl group-containing ester (iii) may be, for example, a compoundof the formula:CHR²¹═CHR³¹wherein R²¹ is a hydrogen atom or COOR⁴¹,

-   R³¹ is COOR⁴¹ or OCOR⁴¹-   (R⁴¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl    group having 3 to 10 carbon atoms, a fluoroalkyl group having 1 to    10 carbon atoms, or a phenyl group which may substituted with an    alkyl group having 1 to 8 carbon atoms. When R³¹ is OCOR⁴¹, R²¹ is a    hydrogen atom.).

Examples of the vinyl group-containing ester (iii) include a vinylcarboxylate of the formula:CH₂═CH(OCOR⁴¹)wherein R⁴¹ is the same as defined above, and

-   a maleate diester or fumarate diester of the formula:    (R⁴¹OOC)CH═CH(COOR⁴¹)    wherein R⁴¹ is the same as defined above.

The vinyl carboxylate is not limited and examples thereof include vinylacetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinylpivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinylstearate, vinyl benzoate, vinyl p-t-butylbenzoate, vinyl salicylate,vinyl cyclohexane carboxylate, vinyl hexafluoropropionate and vinyltrichloroacetate.

The maleate diester and the fumarate diester are not limited andexamples thereof include dimethyl maleate, diethyl maleate, dipropylmaleate, dibutyl maleate, diphenyl maleate, dibenzyl maleate, ditritylmaleate, ditrifluoromethyl maleate, ditrifluoroethyl maleate,dihexafluoropropyl maleate, dimethyl fumarate, diethyl fumarate,dipropyl fumarate, dibutyl fumarate, diphenyl fumarate, dibenzylfumarate, ditrityl fumarate, ditrifluoromethyl fumarate,ditrifluoroethyl fumarate, and dihexafluoropropyl fumarate.

Examples of the vinyl monomer having curing reactive group include vinylmonomers wherein the curing reactive group is a hydroxyl group, acarboxyl group, an epoxy group, a silyl group or the like.

Examples of the vinyl monomer wherein the curing reactive group is thehydroxyl group include the hydroxyalkyl vinyl ether, the hydroxyalkylvinyl ester and the like mentioned as the vinyl group-containing ether(ii).

Specific examples of the carboxyl group-containing vinyl monomer includeone derived from crotonic acid, maleic acid, acrylic acid, methacrylicacid, itaconic acid, vinyl acetate or the like.

Specific examples of the epoxy group-containing vinyl monomer may beones described in JP-A-2-232250 and JP-A-2-232251 and include an epoxyvinyl and an epoxy vinyl ether of the following formula:CH₂═CH—R⁵³—R⁵⁴wherein R⁵³ is

or —R⁵⁵— (wherein R⁵⁵ is an alkylene group), andR⁵⁴ is

(wherein R⁵⁶ is a hydrogen atom or an alkyl group),

Specific examples thereof are as follows:

Specific examples of the silyl group-containing vinyl monomer may beones described in JP-A-61-141713 and include vinyl trimethoxysilane,vinyl triethoxysilane, vinyl tripropoxysilane, vinylmethyldimethoxysilane, vinyl dimethylmethoxysilane, vinylmethyldiethoxysilane, vinyl tris(β-methoxy)silane, trimethoxysilylethylvinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinylether, triethoxysilylbutyl vinyl ether, trimethoxysilylpropyl vinylether, triethoxysilylpropyl vinyl ether, vinyl triisopropenyloxysilane,vinyl methyl diisopropenyloxysilane, triisopropenyloxysilylethyl vinylether, triisopropenyloxysilylpropyl vinyl ether,triisopropenyloxysilylbutyl vinyl ether, vinyltris(dimethyliminoxy)silane, vinyl tris(methylethyliminoxy)silane, vinylmethylbis(methyldimethyliminoxy)silane, vinyldimethyl(dimethyliminoxy)silane, tris(dimethyliminoxy)silylethyl vinylether, methylbis(dimethyliminoxy)silylethyl vinyl ether,tris(dimethyliminoxy)silylbutyl vinyl ether, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyl triethoxysilane,γ-(meth)acryloyloxypropyl methyldimethoxysilane,γ-(meth)acryloyloxypropyl triisopropenyloxysilane,γ-(meth)acryloyloxypropyl tris(dimethyliminoxy)silane,γ-(meth)acryloyloxypropyl tris(dimethyliminoxy)silane and allyltrimethoxysilane.

A polymerization method for producing a copolymer comprising thefluoroolefin monomer and the vinyl monomer is not particularly limitedand may be a conventional method, for example, an emulsionpolymerization, a suspension polymerization, a solution polymerizationand a bulk polymerization which can be suitably selected.

A polymerization reactor, a polymerization method, a polymerizationinitiator, a polymerization inhibitor, and other aids used for thepolymerization, an emulsification aid, a surface active agent and otheradditives used for the emulsion polymerization are suitably selectedfrom the conventional ones. Any of the conventional ones can be selectedfrom the above matters provided that a resultant copolymer is suitable.

A solvent for the polymer prepared by the polymerization is not limited.The solvent is preferably ketones or esters having particularly aboiling point of about 60 to 250° C. in view of solubility. Examples ofthe solvent include acetone, methyl ethyl ketone, methyl i-butyl ketone,cyclohexanone, ethyl acetate, n-butyl acetate, and methyl cellosolveacetate. These can be used alone or in combination of at least two.Other examples of the organic solvent include tetrahydrofuran (THF) anddimethyl formamide (DMF) and aromatic organic compounds such as tolueneand xylene and alcohols may be added. The organic solvent sufficientlydissolves the organic solvent-soluble fluorine-containing resin to givea composition comprising the resin in a wide concentration range betweena low concentration and a high concentration.

An average molecular weight (according to GPC) of thefluorine-containing resin may be from 1,000 to 500,000, particularlyfrom 1,500 to 100,000.

Specific examples of the curable fluorine-containing resin are curablefluorine-containing resins described in, for example, JP-B-60-21686,JP-A-3-121107, JP-A-4-279612, JP-A-4-28707 and JP-A-2-232221.

The fluorine-containing resin may be a blend of at leastfluorine-containing resins. The fluorine-containing resin may be blendedwith one or at least two other resins. Examples of the other resininclude a styrene resin, a (meth)acrylic resin, a polyester resin, analkyd resin, a melamine-formaldehyde resin, a polyisocyanate-basedresin, an epoxy resin, a vinyl chloride resin (for example, a vinylchloride/vinyl acetate copolymer), a ketone resin, a petroleum resin, achlorinated product of polyolefins such as polyethylene andpolypropylene, an inorganic resin such as silica gel and silicate, and afluororesin (for example, a fluoroalkyl group-containing resin) whichdoes not include a fluoroolefin, and the other resin is not limited tothese.

The curing agent is one which reacts with a curing reactive group of thecurable fluorine-containing resin to cure the fluorine-containing resin.Examples of the curing agent include an isocyanate compound, an aminoresin, an acid anhydride, polysilane compound, a polyexpoxy compound andan isocyanate group-containing silane compound.

Non-limiting specific examples of the isocyanate compound include2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylenediisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate,methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate,hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, a trimerthereof, an adduct product and biuret product thereof, a polymer thereofhaving at least two isocyanate groups, and a blocked isocyanate.

Non-limiting specific examples of the amino resin include a urea resin;a melamine resin; a benzoguanamine resin; glycoluril resin; amethylolated melamine resin in which a melamine resin is methylolated;and an alkyl-etherized melamine resin in which a methylolated melamineis etherized with an alcohol such as methanol, ethanol and butanol.

Non-limiting specific examples of the acid anhydride include phthalicanhydride, pyromellitic anhydride and mellitic anhydride.

Examples of the polysilane compound include a compound having at leasttwo groups selected from a SiOH group and a hydrolyzable group directlybonded to a silicon atom; and a condensate of said compound. Forexample, compounds described in JP-A-2-232250 and JP-A-2-232251 can beused as the polysilane compound. Specific examples of the polysilanecompound include dimethyldimethoxysilane, dibutyldimethoxysilane,diisopropyldipropoxysilane, diphenyldibutoxysilane,diphenylethoxysilane, diethyl disilanol, dihexyl disilanol,methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,propyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane,hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol,tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,tetraacetoxysilane, diisopropoxydivaleroxysilane, and tetrasilanol.

Examples of the polyepoxy compound and isocyanate group-containingsilane compound include compounds described in JP-A-2-232250 andJP-A-2-232251. Preferable examples thereof include the followings:

The amount of the curing agent may be from 0.1 to 5 equivalents,preferably from 0.5 to 1. 5 equivalents, based on 1 equivalent of curingreactive group in the curable fluorine-containing resin.

The silicone oil used in the present invention may be any of a straightsilicone oil and a modified silicone oil. Examples of the silicone oilinclude dimethyl silicone, methylphenyl silicone, methylhydrogensilicone, cyclic polydimethylsiloxane, alkyl-modified silicone,alcohol-modified silicone, amino-modified silicone, fluoroalkyl-modifiedsilicone, chloroalkyl-modified silicone, and other organic modifiedsilicones.

Non-limiting specific examples of the silicone oil include thefollowings:

wherein R is an alkylene group having at least one carbon atom,

-   PA is a polyalkylene oxide,-   Rf is a perfluoroalkyl group containing an alkyl group having 4 to    20 carbon atoms,-   x is an integer of 0 or at least 1, and-   y is an integer of at least 1.

Specific examples of the silicone oil are PRX413 (manufactured by DowCorning Toray Silicone Co., Ltd.), SF8417 (ditto), SF8418 (ditto),BY16-855B (ditto), SF8427 (ditto), SF8428 (ditto), FS1265 (ditto),X-22-161C (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-857(ditto), KP-358 (ditto), KP-359 (ditto), X-22-819 (ditto), and FL100(ditto).

The amount of the silicone oil may be from 1 to 50 parts by weight, forexample, 2 to 30 parts by weight, based on 100 parts by weight of thefluorine-containing resin.

If the appearance of matting is necessary according to the applicationsof coated leather, a matting agent can be contained in thefluorine-containing resin paint composition.

The matting agent may be any of inorganic or organic and used incombination of at least two.

Non-limiting specific examples of the matting agent include a silicamatting agent comprising silica fine powder, and an organic mattingagent such as polyethylene or acrylic beads.

The matting agent may be modified for the purpose of increasing thedispersibility.

The amount of the matting agent is generally at most 50 parts by weight,more preferably at most 40 parts by weight, based on 100 parts by weightof the fluorine-containing resin.

The fluorine-containing resin coating composition of the presentinvention may contain various additives. Examples of the additiveinclude, conventionally known, a curing accelerator, a pigment, apigment dispersing agent, a dye, a leveling agent, an antifoaming agent,an antigelling agent, an ultraviolet absorbing agent, an antioxidationagent, a plasticizer, a thickening agent, a rot-proofing agent, afungi-proofing agent, a mildew-proofing agent, and a flame retardant.

Examples of the curing accelerator include an organic tin compound, anacidic phosphate ester, a reaction product between the acidic phosphateester and an amine, a saturated or unsaturated polycarboxylic acid oranhydride thereof, an organic titanate compound, an amine compound, andlead octoate. The curing agent may be used alone or in combination of atleast two.

The amount of the curing accelerator is preferably from about 1.0×10⁻⁶to about 1.0×10⁻² parts by weight, more preferably from about 5.0×10⁻⁵to about 1.0×10⁻³, based on 100 parts by weight of thefluorine-containing resin.

In the present invention, the coating composition may be in the form ofan organic solvent paint, an aqueous dispersion paint or a non-aqueousdispersion paint.

Examples of a solvent used in the organic solvent paint include esterssuch as ethyl acetate, butyl acetate, isopropyl acetate, isobutylacetate, cellosolve acetate, propyleneglycol methyl ether acetate;ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone andcyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; amidessuch as N,N-dimethyl formamide and N,N-dimethyl acetamide; aromatichydrocarbons such as toluene and xylene; alcohols such aspropyleneglycol methyl ether; hydrocarbons such as hexane and heptane; amixture solvent thereof. The concentration of solid components in theorganic solvent paint is from 1 to 95% by weight, preferably from 5 to70% by weight.

The coated leather of the present invention coated with thefluorine-containing resin can be prepared by coating thefluorine-containing resin coating composition on the leather directly orindirectly through a primer layer, and then drying and curing thecomposition.

The primer may be conventional primers for leather. Examples of theprimer include a paint comprising an acrylic resin, a methacrylic resin,a urethane resin, an acrylonitrile resin, a butadiene resin, a styreneresin, a vinyl chloride resin, a vinylidene chloride resin, a vinylacetate resin or a mixture of at least two thereof The formation of theprimer layer improves the smoothness and the uniformity of appearance.The amount of the primer layer coated may be at least 1 g/m², forexample, from 1 to 100 g/m².

The coating amount (solid content) of the fluorine-containing resinpaint film may be at least 2 g/m², for example, from 2 to 100 g/m². Thefluorine-containing resin paint film forms an outermost layer of thecoated leather.

The coating method is not limited, and a spray coating, a brush coating,a curtain coating, a roll coating and the like can be used.

The paint film can be dried and cured usually at 0 to 200° C. for 2 or 3seconds to 10 days. The drying and curing method of the paint film varydepending on types of the curing agent and curing accelerator, a coatingamount, and type of leather and the like. Examples of said drying andcuring method include (1) a method of keeping standing at roomtemperature for at least one day, (2) a method of keeping standing in50° C. hot air dryer for at least 30 seconds, (3) a method of heating byan infrared heating machine for at least 10 seconds.

The leather to be coated may be natural skin or fur, or a leather-likesubstrate. Various leathers may be used. Examples of the leather includea natural leather, and a leather-like material such as an artificialleather, a synthetic leather and a vinyl leather.

Examples of animal from which the natural leather is originated includea cow, a sheep, a goat, a pig, a horse, a kangaroo and a deer. A resinfilm may be laminated on the natural leather.

Examples of the leather-like material include an artificial leather, asynthetic leather, and a vinyl leather. Examples of a surface layerresin for these leathers include a polyurethane resin, a polyvinylchloride resin, a polyolefin resin and nylon.

The fluorine-containing paint film of the present invention hasexcellent transparency so that the paint film is applied directly orthrough a transparent primer layer on the leather, and a surface designof the leather can be utilized. When the primer is mixed with a pigmentto color the primer layer, or when the fluorine-containing resin paintis mixed with the pigment to color the paint, the color of the pigmentcan be vividly shown. The leather coated with the fluorine-containingresin paint of the present invention has excellent soil releasabilityand abrasion resistance and excellent design.

The leather coated with the fluorine-containing resin of the presentinvention can be processed to give various leather products. Examples ofthe leather products are interiors of building constructions; interiorsof vehicles such as a seat, headrest, armrest, steering, door interiorand ceiling interior of an automobile, a seat or interior of anaircraft, a seat of a rail way vehicle, and a seat of a ship; leatherfurniture items such as a sofa, a living chair, a dining chair and atable; leather shoes such as boots, pumps, business shoes, sports shoesand hard shoes; leather bags such as a school child's satchel, ahandbag, a shoulder bag, a porch, a Boston bag and rucksack; leatherclothes such as a skirt, a coat, pants, a jacket, a rider suit, a skiwear, a glove and a cap; leather accessories such as a purse, a belt, awatch band, a pocket diary, a harness and a book cover; and a rawmaterial for handicrafts. The leather product can be prepared by cuttingand sewing the coated leather of the present invention or by shaping theleather in the form of the leather product and then coating the shapedleather.

PREFERRED EMBODIMENTS OF THE INVENTION

The fluorine-containing resin-coated leather of the present invention isillustrated by the following Examples which do not limit the presentinvention. “Part” and “%” in the Examples are respectively “part byweight” and “% by weight”.

EXAMPLE 1

A tetrafluoroethylene/isobutyrene/hydroxybutyl vinyl ether/vinylpivalate (50/25/10/15 wt %) copolymer (resin hydroxyl group value: 60 mgKOH/g) (100 parts) as a curable fluorine-containing resin, ahexamethylene diisocyanate trimer (NCO value of solid content: 20%) (22parts) as a curing agent, a silica fine powder (average particlediameter: 4 μm) (15 parts) as a matting agent, and an amino-modifiedsilicone oil (10 parts) as a silicone oil were dispersed in 900 parts ofbutyl acetate to give a curable fluorine-containing resin paintcomposition.

This composition (200 g) was coated by a spray gun on a cow hide (1 m²)coated with a commercial leather primer urethane resin paint, and heatedat 50° C. for 2 minutes to give a fluorine-containing resin-coatedleather having an outermost fluorine-containing resin film layer.

The fluorine-containing resin-coated leather prepared in Example 1 wasevaluated in the following methods. Results are shown in Table 1.

(1) Matteness Degree

A 60 degree specular gloss degree of a surface of the coated leather ismeasured by a gloss meter according to JIS K5400. The lower the glossdegree is, the higher the matteness degree is.

(2) Feeling

The softness feeling of the coated leather is evaluated by touch feelingaccording to the following criteria.

-   A: Very soft-   B: Soft-   C: Medium-   D: Hard-   E: Very hard    (3) Soil Releasability

The soil material described below is attached to a surface of the coatedleather and kept for 30 minutes.

Then, a cotton fabric is soaked with a 30 wt % aqueous solution of acommercial kitchen neutral detergent and the soil deposited on thecoated leather is lightly wiped by the cotton fabric. The state of theresidual soil on the leather surface is evaluated according to thefollowing criteria.

-   A: Soil can be removed very easily.-   B: Soil can be removed.-   C: Soil remains in a small amount.-   D: Soil remains in an about half amount.-   E: Soil remains in an almost amount.    Soil Materials:

Lipstick: “CALIFORNIA COLORS NO. 4” manufactured by Nihon Kolmar Co.,Ltd. Ball point pen: Oily ball point pen (black) manufactured byMitsubishi pencil Co., Ltd.

(4) Abrasion Resistance

The coated leather is rubbed with an abrasion wheel CS-10 by a Taberabrasion tester and the surface state is visually observed every 1,000revolutions.

The number of revolutions, at which the abrasion is observed on thecoating film, is measured.

The larger the number of revolutions is, the higher the abrasionresistance is.

EXAMPLE 2

The same procedure as in Example 1 was repeated except that the amountof the matting agent was changed to 30 parts to give afluorine-containing resin-coated leather.

Results are shown in Table 1.

COMPARATIVE EXAMPLES 1 AND 2

The same procedures as in Examples 1 and 2 were repeated except that thesilicone oil was not added to give a fluorine-containing resin-coatedleather control.

Results are shown in Table 1.

COMPARATIVE EXAMPLE 3

The same procedure as in Example 1 was repeated except that acommercially available paint additive for leather (a hydrocarbon oil)was used instead of the silicone oil to give a fluorine-containingresin-coated leather control.

Results are shown in Table 1.

TABLE 1 Example Comparative Example 1 2 1 2 3 Matteness 4 2 4 2 4 degree(gloss degree) Feeling A A C E B (A-E) Soil resistance A B B E E (A-E)Lipstick Soil resistance A B B E E (A-E) Ball point pen Abrasion 5,0005,000 3,000 1,000 3,000 resistance (revolution number)

1. A paint composition for leather, comprising 100 parts by weight of afluorine-containing resin, 1 to 50 parts by weight of a silicone oil,and a matting agent, wherein the matting agent is present in an amountof at most 50 parts by weight of the matting agent based on 100 parts byweight of the fluorine-containing resin, wherein the fluorine-containingresin is a polymer of at least one fluoroolefin monomer or a polymer ofat least one fluoroolefin and at least one vinyl monomer, wherein thefluoroolefin monomer is at least one selected from the group consistingof chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE),trifluoroethylene (TrFE), hexafluoropropylene (HFP), vinylidene fluoride(VDF) and vinyl fluoride (VF), and wherein the silicone oil is at leastone selected from the group consisting of dimethyl silicone,methylphenyl silicone, methylhydrogen silicone, cyclicpolydimethylsiloxane, alkyl-modified silicone, alcohol-modifiedsilicone, amino-modified silicone, fluoroalkyl-modified silicone,chloroalkyl-modified silicone, and other organic modified silicones. 2.The paint composition according to claim 1, wherein the matting agent ispresent in an amount of from 15 to at most 50 parts by weight of thematting agent based on 100 parts by weight of the fluorine-containingresin.
 3. A paint composition for leather, comprising 100 parts byweight of a curable fluorine-containing resin, a curing agent in theamount of 0.1 to 5 equivalents per 1 equivalent of a curing reactivegroup in the curable fluorine-containing resin, 1 to 50 parts by weightof a silicone oil, and a matting agent, wherein the matting agent ispresent in an amount of at most 50 parts by weight of a matting agentbased on 100 parts by weight of the curable fluorine-containing resin,wherein the curable fluorine-containing resin is a polymer of at leastone fluoroolefin monomer or a polymer of at least one fluoroolefin andat least one vinyl monomer, wherein the fluoroolefin monomer is at leastone selected from the group consisting of chlorotrifluoroethylene(CTFE), tetrafluoroethylene (TFE), trifluoroethylene (TrFE),hexafluoropropylene (HFP), vinylidene fluoride (VDF) and vinyl fluoride(VF), and wherein the silicone oil is at least one selected from thegroup consisting of dimethyl silicone, methylphenyl silicone,methyihydrogen silicone, cyclic polydimethylsiloxane, alkyl-modifiedsilicone, alcohol-modified silicone, amino-modified silicone,fluoroalkyl-modified silicone, chloroalkyl-modified silicone, and otherowanic modified silicones.
 4. The paint composition according to claim3, wherein the curable fluorine-containing resin contains a curingreactive group.
 5. The paint composition according to claim 4, whereinthe curing reactive group of the curable fluorine-containing resin is atleast one selected from the group consisting of a hydroxyl group, anamino group, an epoxy group, a carboxyl group, a mercapto group, ahydrolyzable silyl group, an amide linkage, a urethane linkage and aurea linkage.
 6. The paint composition according to claim 3, wherein thecuring agent is selected from the group consisting of an isocyanatecompound, an amino resin, an acid anhydride, polysilane compound, apolyexpoxy compound and an isocyanate group-containing silane compound.7. The paint composition according to claim 3, wherein the matting agentis present in an amount of from 15 to at most 50 parts by weight of thematting agent based on 100 parts by weight of the fluorine-containingresin.
 8. The paint composition according to claim 1 or 3, wherein thevinyl monomer to be copolymerized with the fluoroolefin monomer isselected from the group consisting of (i) a β-methyl-β-alkyl-substitutedα-olefin, (ii) a vinyl group-containing ether, and (iii) a vinylgroup-containing ester.
 9. The paint composition according to claim 1 or3, wherein the matting agent is inorganic, organic or a combinationthereof.
 10. The paint composition according to claim 1 or 3, whereinthe matting agent is at least one selected from the group consisting ofa silica matting agent comprising silica fine powder, a polyethylenebeads matting agent and an acrylic beads matting agent.
 11. A method ofproducing a coated leather, which comprises coating the paintcomposition according to claim 1 on a leather.
 12. A coated leatherproduced by the method according to claim
 11. 13. The coated leatheraccording to claim 12, wherein the leather is a natural leather or anartificial leather.
 14. The coated leather according to claim 12, whichforms part of an interior of a building construction, an interior of avehicle, a furniture item, a shoe, a bag, clothes and a leatheraccessory.
 15. A method of producing a coated leather, which comprisescoating the paint composition according to claim 3 on a leather.
 16. Acoated leather produced by the method according to claim
 15. 17. Thecoated leather according to claim 16, wherein the leather is a naturalleather or an artificial leather.
 18. The coated leather according toclaim 17, which forms part of an interior of a building construction, aninterior of a vehicle, a furniture item, a shoe, a bag, clothes and aleather accessory.